An All-Organic Photochemical Magnetic Switch with Bistable Spin States

Controlling the electronic spin state in single molecules through an external stimulus is of interest in developing devices for information technology, such as data storage and quantum computing. We report the synthesis and operation mode of two all-organic molecular spin-state switches that can be photochemically switched from a diamagnetic [electron paramagnetic resonance (EPR)-silent] to a paramagnetic (EPR-active) form at cryogenic temperatures due to a reversible electrocyclic reaction of its carbon skeleton. Facile synthetic substitution of a configurationally stable 1,14-dimethyl-[5]helicene with radical stabilizing groups at the 4,11-positions afforded two spin-state switches as 4,11-dioxo or 4,11-bis(dicyanomethylidenyl) derivatives in a closed diamagnetic form. After irradiation with an LED light source at cryogenic temperatures, a stable paramagnetic state is readily obtained, making this system a bistable magnetic switch that can reversibly react back to its diamagnetic form through a thermal stimulus. The switching can be monitored with UV/vis spectroscopy and EPR spectroscopy or induced by electrochemical reduction and reoxidation. Variable-temperature EPR spectroscopy of the paramagnetic species revealed an open-shell triplet ground state with an experimentally determined triplet-singlet energy gap of ΔET-S < 0.1 kcal mol-1. The inherent chirality and the ability to separate the enantiomers turns this helical motif into a potential chiroptical spin-state switch. The herein developed 4,11-substitution pattern on the dimethyl[5]helicene introduces a platform for designing future generations of organic molecular photomagnetic switches that might find applications in spintronics and related fields.